Water repellent, method of impregnating textiles with same, and textiles bearing same



dency to form a stable or thick foam.

United States Patent '0 2,981,704 7 1 WATER REPELLENT, METHOD OF IMPREGNAT- ING TEXTILES WITH SAME, AND TEXTHJES BEARING SAME William F. Herbes, Somerville, and Andrews C. Winn-ingham, Glen Ridge, N.J., assignors to American Cyanar'nid Company, New York, N.Y., a corporation of Maine No Drawing. Filed Apr. 12, 1956, Ser. No. 577,673 17 Claims. (Cl. 260-21) The present invention relates to an improved waterrepellent composition, its preferred use in treating textile fabrics and the resultant durably water-repellent fabrics.

Many agents have been suggested for producing a water-repellent finish on various textile fabrics. Com paratively few of these have been commercially successful and many of these are of a nondurable. or impermanent nature in that they are removed readily upon washing or dry cleaning. The number ofwater-repellent agents of a durable nature, that is, capable of standing repeated washing or dry cleaning, isstill smaller. Among those which have achieved outstanding commercial recognition inthe' textile finishing field are those disclosed in Thurston Patent No. 2,357,273. Thurstons dispersions comprise essentially an alkylated methylol melamine such as methylated methylol melamine in combination with certain reactive nitrogenous compounds containing a higher alkyl radical as exemplified by stearamide and methylol stearamide and although they have consistently produced excellent and durable water repellency on cotton and other textile fabrics, certain difliculties and limitations attend their use. They have a marked tendency toward foaming, and thisfoam is of a dry and stable nature that tends to build up and create difiiculties in the pad baths of textile finishing plants. Occasionally, the foam is carried along with the goods being padded which results in spotting, and this sometimes produces a spotted appearance on the treated fabric. In addition, these water-repellent compositions are incompatible with a number of other dispersible and/ or soluble textile treating agents such as magnesium chloride, certain dyeing assistants and/or dye fixatives, textile softeners of the type described in Patent No. 2,427,242, and with hard water. This incompatibility manifests itself in the form of separation of the bath constituents or the formation of a creamy layer which spoil the bath for textile treating piuposes. Magnesium chloride is currently regarded as the most effective catalyst for-curing resinous compositions containing melamine as (1) it greatly reduces the chlorine retention of melamine-formaldehyde treated fabrics, and (2) it greatly improves the efiiciency of the resin. 1

An object of the invention is toprovide an improved water-repellent composition. 1

Another object of the invention is to" provide an improved method for producing water-repellent effects on various textile fabrics.

fabrics having an improved durable nature.

Still another object of the invention is to provide an improved water-repellentcomposition of greater 'com patibility with other substances used in the treatment of VA still further object of the invention is toprovide an;

textiles.

improved water-repellent composition having less ten- Other objects and advantages of the invention will be apparent-upon consideration ofthe detailed disclosure .hereinbelow gy r The present invention accordingly concerns aqueous dispersions of one or more of certain selected thermosetting resins, one or more compounds having an alkyl radical of at least 7 carbon atoms and containing a nitrogen atom having attached thereto a carbonyl radical and a reactive substituent of the group consisting of hydrogen and alkylol radicals, one or more of certain alkali soaps, and one or more of certain selected nonionic stnface active agents; and also the treatment of textile materials therewith and the resulting durably water-repellent articles. Optional constituents of the above dispersions, which are highly desirable for many purposes, include certain anionic surface-active agents. The preferred resins are methylated methylol melamine resins. 7

Unless otherwise designated herein, such expressions as long chain or higher alkyl radicals, aliphatic fatty acids and like expressions are used to refer to chains of at least 7 carbon atoms, and especially those containing between about 12 andabout 22 carbon atoms, on up to 30 or more carbons in the chain. 1 i

The present invention constitutes an improvement over that-disclosed in the Thurston patent, especially in connection with the addition of certain selected nonionic dispersing agents but also in the wider range of equivalent therrnosetting resin components and the stabilizing effect of certain sulfonated or. sulfated surface-active agents. None of the difficulties described earlier are encountered with the present dispersions, and a definitely improved resistance to spotting has been observed. The tendency toward foaming in commercial pad baths is greatly reduced as any foam formed has been found to be of a wetter nature which breaks more easily. Moreover, the present compositions are not substantially affected by dilution with hard water, and they are compatible with the aforementioned softener as well as the important class of dyei fixatives of the basic cationic complexes. Although dyeing operations are carried out in advance of the present treatment, residual amounts of such copper complexes frequently remain on textile fabrics evenafter an. intervening washing. In addition, many compositions of the presentinvention are suitable foruse with the highly effective magnesium chloride curing catalyst. Besides those mentioned, other benefits obtained in treating textile fabrics with the present compositions are improved 1 abrasion and wear resistance, felting of the fabrics, spot resistance, mildew resistance, durable wrinkle recovery, dimensional stability, maximum tear strength and sewability, reduction of stretching and sagging, longer fabric life and reduction of fabric shift and yarn slippage.

various blendsthereof, However, the greatest utility and the preferred materials are those containing cellulose fibers such as cotton, viscose and cuprammonium rayons, I

linen, hemp, jute and ramie, either alone or mixed in I a substantial proportion amountingto at least: about 25% 1 by Weight with other textile fibers.

The hydrophobic nitrogen-containingcompounds used in preparing the present water repellent are those ,described in the aforesaid .patentand having the' general fO mulai 1 :1 m.

@xz tel s.

in which Y is a member of the group consisting of hydrogen and unsubstituted or substituted alkylol radicals, such as methylol or ethylol radicals, Z is a member of the group consisting of oxygen and sulfur, and X and R are members of the group consisting of hydrogen, nonfunctional substituents, and radicals containing alkyl hydrophobe groups of at least 7 carbon atoms, it being understood that in all cases at least one X or R contains a hydrophobe alkyl radical of at least 7 carbon atoms.

Thurston names a wide range of suitable equivalents which need not be repeated here in full detail except to mention that the preferred groups are the amides of monocarboxylic higher fatty acids like caprylamide, capramide, lauramide, palmitamide, stearamide, and theamides of unsaturated acids such as oleic: acid, linoleic acid, ricinoleic acid, etc. Optimum results have been obtained with the saturated higher fatty acids such as stearamide and especially with their N-methylolderivatives.

The resin-forming constituents of the novel compositions include alkylated methylol melamines, alkylated methylol ureas, and methylol alkylene ureas. Of these, the methyl ethers of methylol melamine provide the optimum results, and such may contain from 1 to 6 mols of combined formaldehyde and l to 6 mols of combined methanol per mol of melamine; the combined methanol, of course, doesnot exceed the combined formaldehyde on a molar basis. Typical examples are a 67% methylated trimethylol melamine anda 50% methylated pentamethylol melamine and the alkylated methylol ureas. This term (alkylated methylol ureas) is used herein in its broader sense to include both monomers and their water-soluble low order polymers inasmuch as both are operative. Of these, the partially polymerized methoxy methyl ureas are preferred. Other suitable agents include formaldehyde condensates of alkylene ureas like dimethylol ethylene urea, dimethylol propylene urea, and dimethylol trimethylene urea. These substances and their preparation are well understood and they may contain from 1 to 2 mols of combined formaldehyde per mol of urea or urea derivative as well as a combined methanol content ranging from about up to but not exceeding.

'etc.), the resins described herein maybe introduced in' an amount ranging between about and about 100 parts and, preferably between about and about 200 parts. Mixtures of resins are also suitable as for instance, methylated trimethylol melamine, and dimethylol ethylene urea in a 2:1 weight ratio and 50% methylated pentamethylol melamine and-methylated methylol urea in equal weights.

Another component of the present mixtures is a soap of an alkali metal such, as sodium or'potassium with one or more of the higher fatty acids. The other alkalies such as'an' organic amine like triethanolamine are also contemplated for the purpose and'are included within the,

definitionof alkali soaps here. The quantity of these soaps appears to be relatively critical since too little has an adverse effect on the stability of aqueous dispersions of the products of this invention and too much tends to produce a rewetting effect on treated-cloth which reduces ts, water repellency. Thus, such soap should be present 111 amounts ranging between about 4.5 and about 11 parts based onlOO parts by weight of the hydrophobic nitrogen component. A substantial proportion of the required soap is often formed in. situ from the free' higher fatty acids like lauric, myristic and stearic which are frequently contained in commercially available hydrophobic nitrogen compounds like stearamide. By the addition of a suitable quantity of sodium or potassium hydroxide, an alkali metal soap is formed within the concentrated aqueous dispersion. However, it-is frequently necessary to add an additional quantity of free stearic acid to produce a sufficient quantity of soap.

Nonionic agents suitable for the present invention cornprise water-dispersible higher fatty acid esters of sorbitan and more importantly, the nonionic surface-active condensates of an alkylene oxide (propylene oxide or preferably ethylene oxide) with a water-insoluble substance such as the alkyl phenols; higher fatty acids, higher fatty acid esters of sorbitan and higher fatty acid esters of sorbitol. It is to be emphasized that not all nonionic agents are operative to obtain the improved results. The optimum efliects are obtained with the alkyl phenols condensed with a plurality of mols-of ethylene oxide as for instance, 5 to 50 mols of the latter. Suitable alkyl phenols for preparing these condensates contain from about 7 to about 30 or more carbon atoms in straight or branched chains and excellent examples include octyl phenol, nonyl phenol, lauryl phenol, and octadecyl phenol. The higher fatty acids employed in preparing the aforesaid esters and condensates in known manner may contain from about 8 to about 30 carbon atoms and preferably from about 12 to about 22 carbon atoms as exemplified by lauric, myristic, palmitic, stearic, oleic, ricinoleic, etc. A few of the many operative dispersing agents are the polyoxyethylene derivatives of sorbitan monostearate or monooleate, polyoxyethylenesorbitol laurate or laurate-oleate. These emulsifiers are desirably present in between about 2 and about 20 parts based on parts of the hydrophobic nitrogenous compound.

Optionally and desirably, a sulfonated or sulfated oil may be introduced into the present compositions, preferably in an amount ranging between about 2 and about 15 parts based on 100 parts of said hydrophobic nitrogenous compound. These anionic surface-active materials are produced in known fashion by sulfating or sulfonating either an aliphatic long chain hydrocarbon such as those derived from petroleum oils or the commercial liquid oils from vegetable, marine and animal sources. Coconut, palm, olive, peanut and menhaden may be named as only a few of the suitable oils.

In the present compositions, it is desirable to maintain the total quantity of surface-active components including soap between about 10 and about 35 parts by weight per 100 parts of said hydrophobic nitrogenous compound in order to maintain a dispersion of good stability in either concentrated or dilute form without impairing the waterrepellent effects obtained in treating textile fabrics or other materials. I

While the'compositionshereinbelow'are usually prepared as concentrated aqueous dispersions andsold in such form, as for instance, with solid concentrations. be tween about 30 and about. 60% by weight, it .is desirable to dilute them to between about 0.5 and about 20% solids for application by means of pad baths, spraying or any other suitable means of impregnating textile materials. The textile fabrics are thereafterdried in the usual fashion and cured, and this is most desirably accomplishedin a single operation for about 45 seconds to about 20 minutes at a temperature between about 409 and.

about 2759 F.

The pickup of solids'on'the treated fabrics may be.

varied considerably between about 0.5 and about 20% depending on the effect desired. Light pickups are suitable for providing resistance .to spotting or for modification of hand, but for the full. Waternepellent erTect, the

solids pickup should be betweenaboutl and about 10%. I

A wide variety of catalysts may be used in conventional amounts. ranging between'3 and 4 0% based ehthe weight of thermosetting resin component. Among themany'suit': j

panying illustrative examples in which all proportions are set forth in terms of weight unless otherwise stated therein. These examples are intended for purposes of illustration and comparison rather than as limiting as to proportions and ingredients.

Example 1 1,710 parts of methylated trimethylol melamine (80% solids), 424 parts of 37% formaldehyde, 1,360 parts of stearamide powder containing 47.6 parts of stearic acid, and 27.2 parts of stearic acid are mixed with stirring until a uniform dispersion is obtained. Then 76 parts of a petroleum sulfonate dissolved in 567 parts of water is addedto the dispersion followed by 22.5 parts of potassium hydroxide dissolved in 200 parts of water. This mixture is stirred until smooth, then passed through a heat exchanger equipped with stirring blades at about 104 0., followed by cooling by similar heat exchange means to a temperature of about 25 C. to 35 C. 635 parts of this paste is diluted with a solution containing 13.2 parts of nonyl phenol ethylene oxide adduct (1:9 molar ratio) and 365 parts of water. The mixture is stirred until smooth.

Ten parts of the finished paste are diluted with 80 parts of water. To this dispersion is added 0.2 part of dicyandiamide and 1.6 parts of a 30% solution of magnesium chloride (MgCl The pH of the dispersion is adjusted to 6.0 with a solution of NaH PO The dispersion is then made up to a total of 100 parts with water. This dispersion is applied by padding to cotton poplin, viscose rayon challis, cellulose acetate and 50:50 viscose-acetate fabrics which are then passed between rubber squeeze rolls to give .a wet pickup of approximately 80%. The treated fabrics are dried and then cured'by heating for 90 seconds at 350 P. All of the heat-cured fabrics display a high degree of water repellency ,which is durable to washing and to dry cleaning. j l

A second pad bath is prepared by diluting 10 parts of l the finished paste with 84.8 partsof water. To this dispersion is added 02 part of dicyandiamide and 5 parts of a 20% solution of ammonium sulfate as the curing catalyst. The dispersion is applied to all of the fabrics described above. These. treated fabrics have finishes with substantiallythe same water repellency and durability tovvashing and to dry cleaning.

7 Example. 2

Example .1 is repeated using 13.2,parts of polyoxyethyl-i ene sorbitan mono-oleate, a nonionic surface-active agent, in place of the nonionic adduct.

The finished paste is applied tocotton poplin and rayon challis as before. The finisheson these cured fabrics are almost equal in durability and water-repellent characteristics tothose obtained inthe preceding example; i s

l Comparative ExampleA s The procedure of Example 1 repeated substituting. 13.2 parts. of. a well-known nonionic polyoxyalkylene ether, of a higher alkyl branched chain alcohol dispersing agent in place of, the nonyl phenol-ethylene oxide cone} densate. 1 The finished paste is made into two pad baths as 6 s Comparative Example B s s Again the procedure of Example. 1 is duplicated with 13.2 parts of a different nonionic surface-active agent, namely, the condensateof ethylene oxide with a hydrophobic compound formed by condensing propylene oxide with propylene glycol, in place of the adduct of nonyl phenol with ethylene oxide. This composition is unsatisfactory as a waterproofing agent because a pad bath made with ammonium sulfate as the catalyst shows flocculation and separation.

Example 3 Again a composition is compounded according to Example 1 with 13.2 parts of nonionic polyethylene glycol 600 monolaurate replacing the aforesaid nonionic adduct. The finished paste is applied in the same maner to samples of cotton poplin and rayon challis using ammonium sulfate as the catalyst. The treated fabrics have a durable finish with a good spray rating.

Example 4 The composition of Example 1 is changed by the selection of 13.2 parts of polyoxyethylene sorbitol oleatelaurate asthe non-ionic surface-active agent. Upon applying the paste in an ammonium sulfate catalyzed pad bath as before to cotton poplin and rayon from the same source, the fabrics after curing are found to have good water-repellent characteristics in a finish which is durabl to dry cleaning and washing.

Example 5 Example 6 A water-repellentagent is compounded as in Example 1 with a different resin component. An 80%, aqueous dispersion of methylated partially polymerized dimethylol urea 80% of the methylol groups being methylated) isused in lieu of the same weight 1of methylated trimethylol melamine on an equivalent solids basis. After treating the same cotton poplin and rayon challis according to Example 1 in a pad bath containing ammonium sulfate, the resulting textile products are found to have good water-repellent characteristics in the durable finish.

Exampl e 7- l s f A water-repellent composition is compounded according to Example 1 with 19 parts of lauric acid substituted inplace of 27.2 parts of the stearicfacid used therein; No. substantial change results in observed on any of the .treatedfabrics using both catalysts. Example 8 V Example 1 is repeated in full using the composition wherein 27:1 parts of oleic acid are employed instead of 27.2 parts of stearic acid. The characteristics ofthe s Example 9 Ten partsof the finished, paste prepared as described previously. described, using. magnesium chloride, and am- I in Example 1 is diluted with 428 parts of water. To,

thisdispersion is added 0.2 part of dicyandiamide,j42 parts of a solution containing 2 parts of a basicfcation activecoppercornplex compound and 40 parts of,water,;

and 5 parts of.a l20% solution of ammoniuni sulfate 9999 thespia an i d t swan marlin. aid it 1 Example 2,710 parts of .dimethylol ethylene urea (50% solids), 424 parts of 37% formaldehyde, 1,360 parts of stearamide powder containing 47.6 parts of stearic acid and 27.2 parts of stearic acid are mixed with stirring until a uniform dispersion is obtained. 76 parts of a petroleum sulfonate is dissolved in 567 parts of water and this solution is added to the dispersion. 22.5 parts of potassium hydroxide is, dissolved in 200parts of water and this solution is also added to the dispersion. The mixture is stirred until smooth, and heated and cooled as in Example 1. 1,270 parts of the paste is diluted with a solution containing 26.4 parts of nonyl phenol ethylene oxide adduct and 730 parts of water. The mixture is stirred until smooth.

10 parts of the finish paste is diluted with 84.8.parts of water. To this dispersion is added 0.2 part of dioyandiamide. and 5 parts of a% solution of ammonium sulfate. The; dispersion is applied as before ,to cotton poplin. The treated fabric shows good water repellency which is durable to repeated washing and to dry cleaning.

No difliculties with foaming are experienced with the pastes and pad baths in any of the above detailed examples. Any foam encountered is of a thin, wet and relatively unstable nature which does not tend to build up.

While there are above disclosed only a limited number of embodiments of the composition, process and article of the invention herein presented, it is possible to produce still other embodiments without departing from the inventive concept set forth, and it is desired, therefore, that only such limitations be imposed on the appended claims as. are stated therein or required by the prior art.

We claim: i

l. A composition of matter which comprises an aqueous dispersion of from about 40 to about 1000 parts by weight of a thermosetting resin of the group consisting of water soluble alkylated methylol melamines, water soluble alkylated methylol ureas, and methylol alkylene ureas; 100 parts by weight of a hydrophobic nitrogenous compound having an alkyl radical of at least 7 carbon atoms and containing a nitrogen atom having attached thereto a carbonyl radical and a reactive substituent of the group consisting of hydrogen and alkylol radicals joined to said nitrogen atom; about 4.5 to about 11 parts by weight of an alkali soap of a higher'fatty acid containing between 7 and about 30 carbon atoms; and between about 2 and about 20parts by weight of a nonionic surface-active agent of the group consisting of waterdispersible higher fatty acid esters of sorbitan, condensates of between 5 and 50 .mo1s "of ethylene oxide with a Water-insoluble alkyl phenolwherein the alkyl group contains between '7 and 30 carbon atoms, condensates of between 5, and 50; mols of. ethylene oxide with higher fatty-acidsoffromabout B'to about 30 carbon atoms, condensates of from between 5 and 50 mols of ethylene oxide with from about 8 to. about 30 carbon atom higher fatty acid esters 'of-sorbitan, condensates of between 5 and "SOfrnols of, ethylene oxide with from about 8 to about 30j'carbon atom higher fatty acid esters of sorbitol wherein all partslby weight are relative with respect to 100 parts by weight of said hydrophobic nitrogenous compound. I i

2. A composition of matter which comprises an aque ousalkaline dispersion of relative amounts of 100 parts by weightof an N-methylolamide of a higher fatty acid, between about 40 and about 1000 parts by weight of a'methylolated methylol melamine, between abou't*4 .5 and aboutll parts by weight of an alkali metal soap of a highe'rifatty acid containing between 7. and about 30 car-bon'ato m s; between about-2 and about 15 parts by weight of-a surface-active higher alkylsulfonate, and:

between about 2 and about 20 parts by weight of. a nonionic surface-active polyoxyethylene condensatevof an alkyl phenol, wherein the condensate contains from between 5 and 50 mols of ethylene oxide and wherein the alkyl group contains between 7 and about 30zcarbon atoms. p

3. A composition of matter which comprises an alkaline aqueous dispersion of relative amounts of parts by weight of N-methylol amide of a higher fatty acid, between about 40 and about 1000 parts of methylolatcd methylol melamine, between about 4.5 and about 11 parts of an alkali metal soap of a higher fatty acid having between 7 and about 30 carbon atoms, between about 2 and about 15 parts of a surface-active higher alkyl sulfonate, and between about 2 and about 20, parts of a non-ionic surface-active polyoxyethylene condensate of an alkylphenol, wherein the condensate contains from between 5 and 50 mols of ethylene oxide and wherein the alkyl group contains between 7 and about 30 carbon atoms, in "which the total content of the surface-active substances amounts to between 10 and 35 parts.

4. An alkaline aqueous dispersion according to claim 1 in which the thermosetting resin comprises methylated methylol melamine.

5. 'An alkaline aqueousdispersion according to claim I in which the thermosetting resin comprises partially polymerized methylated methylol urea.

. 6. A composition of matter according to claim 1 comprising an anionic surface-active agent of the group consisting of sulfonated oils and sulfated oils.

7. A composition of matter according to claim 1 in which said nonionic agent is a water-soluble, surfaceactive condensate of ethylene oxide with a long chain alkyl phenol wherein the alkyl group contains from between 7 and about 30 carbon atoms.

8. A composition of matter according to claim 1 in which said nonionic agent is a water-soluble surfaceactive condensate of ethylene oxide with a fatty acid monoester of sorbitan.

9. A composition of matter according to claim 1 in which said nonionic agent is a water-soluble condensate of ethylene oxide with along chain alkyl phenol and also containing an anionic. surface-active agen't of the group consisting of sulfonated oils and sulfated oils.

"10. A process which comprises impregnating a textile material With'a composition according to claim 1 and heating the impregnated material'to cure the finish to the substantially water-insoluble state whereby a-durable water-repellent finish is imparted to, the textile material. 11. A process which .comprises impregnating a textile material with a composition of'matter accordingto claim l'in the presence of magnesium chloride and heating the impregnated material to cure the finish to the substantially water-insoluble state whereby a durable waterrepellent finish is imparted to the textile material.

l2. A process which comprises, impregnatinga textile material with a composition according to'claim 2- in the presenceof between about 4.5 and about 24 :pe'r'cent of magnesium chloride based on the weight of methylated methylolymelamine' and heating the impregnated fabric to curethe finish to the substantially water-insoluble state whereby a, durable water-repellent firiish is imparted to the textile material.

13; A process whichcomprises impregnating a textile material containing cellulose fibers with a composition according to claim 3 in the presence of between about 9- and about-1 5 percent of magnesium chloride'bas'ed on the weight-of methylatedinethylol melamine and heat ing the impregnated. fabric tocure the finish to the substantially water-insoluble state whereby [a durable water-repellent finish is imparted. to the textile'rnaterial, 14.- A process which comprises" impregnating a "textile material bearing; a dyefixative of the group consisting "of" basicwcation-active copper cbmplex compounds witha. .composition" according to claim .1 and'heatingtheirnpregnated material to cure the finish to the substantially water-insoluble state whereby a durable Water-repellent finish is imparted to the textile material.

15. An article which comprises a durably water-repellent textile material bearing the waterinsoluble product of curing a composition according to claim 1 with magnesium chloride.

16. An article which comprises a durably waterrepellent textile material bearing the water-insoluble product of curing a composition according to claim 2 with magnesium chloride.

17. An article which comprises a durably waterrepellent textile material bearing the Water-insoluble prodnet of curing a composition according to claim 3 with magnesium chloride.

References Cited in the file of this patent UNITED STATES PATENTS 2,357,273 Thurston Aug. 29, 1944 10 2,364,726 Landolt Dec. 12, 1944 2,491,249 Cathers et al. Dec. 13, 1949 2,528,360 Greenlee Oct. 31, 1950 2,683,702 Eastes et al. July 13, 1954 2,749,257 Knnp June 5, 1956 2,767,434 Fortune Oct. 23, 1956 2,769,798 Meis et al. Nov. 6, 1956 2,776,267 Weber Jan. 1, 1957 2,846,337 Cooke et al. Aug. 5, 1958 2,852,479 Bender et al. Sept. 16, 1958 FOREIGN PATENTS 506,408 Canada Oct. 12, 1954 OTHER REFERENCES Speel: Textile Chemicals and Auxiliaries, pp. 260-1, pp. 318-327, 331-2, 410-411, 466, Reinhold (1952). 

1. A COMPOSITION OF MATTER WHICH COMPRISES AN AQUEOUS DISPERSION OF FROM ABOUT 40 TO ABOUT 1000 PARTS BY WEIGHT OF A THERMOSETTING RESIN OF THE GROUP CONSISTING OF WATER SOLUBLE ALKYLATED METHYLOL MELAMINES, WATER SOLUBLE ALKYLATED METHYLOL UREAS, AND METHYLOL ALKYLENE UREAS, 100 PARTS BY WEIGHT OF A HYDROPHOBIC NITROGENOUS COMPOUND HAVING AN ALKYL RADICAL OF AT LEAST 7 CARBON ATOMS AND CONTAINING A NITROGEN ATOM HAVING ATTACHED THERETO A CARBONYL RADICAL AND A REACTIVE SUBSTITUENT OF THE GROUP CONSISTING OF HYDROGEN AND ALKYLOL RADICALS JOINED TO SAID NITROGEN ATOM, ABOUT 4.5 TO ABOUT 11 PARTS BY WEIGHT OF AN ALKALI SOAP OF A HIGHER FATTY ACID CONTAINING BETWEEN 7 AND ABOUT 30 CARBON ATOMS, AND BETWEEN ABOUT 2 AND ABOUT 20 PARTS BY WEIGHT OF A NONIONIC SURFACES-ACTIVE AGENT OF THE GROUP CONSISTING OF WATERDISPERSIBLE HIGHER FATTY ACID ESTERS OF SORBITAN, CONDENSATES OF BETWEEN 5 AND 50 MOLS OF ETHYLENE OXIDE WITH A WATER-INSOLUBLE ALKYL PHENOL WHEREIN THE ALKYL GROUP CONTAINS BETWEEN 7 AND 30 CARBON ATOMS, CONDENSATES OF BETWEEN 5 AND 50 MOLS OF ETHYLENE OXIDE WITH HIGHER FATTY ACIDS OF FROM ABOUT 8 TO ABOUT 30 CARBON ATOMS, CONDENSATES OF FROM BETWEEN 5 AND 50 MOLS OF ETHYLENE OXIDE WITH FROM ABOUT 8 TO ABOUT 30 CARBON ATOM HIGHER FATTY ACID ESTERS OF SORBITAN, CONDENSATES OF BETWEEN 5 AND 50 MOLS OF ETHYLENE OXIDE WITH FROM ABOUT 8 TO ABOUT 30 CARBON ATOM HIGHER FATTY ACID ESTERS OF SORBITOL WHEREIN ALL PARTS BY WEIGHT ARE RELATIVE WITH RESPECT TO 100 PARTS BY WEIGHT OF SAID HYDROPHOBIC NITROGENOUS COMPOUND. 